Conversion of hydrocarbons



MWA, 1937. E. .1. HQUDRY CONVERSION oF HYDRocARBoNs Filed Aug. 31, 195s 5 Sheets-Sheet l Filed Aug. 31, 1933 3 Sheets-'Sheet 2 MVM@ mWQ/ww l ATTORNEY May 4,' 195m E. J. HfOUD-RY .2,078,945

CONVERSION OF HYDROCARBONS Filed Aug. 51, 1955 5 'sheets-sheet 5 PatentedMay, 1937vl l PATE-NT. OFFICE i 2,078,946 coNvERsIoN oF HYDRocARBoNs Eugene J. Houdry, Woodbury, N. J., assignor to Houdry Process Corporation, Dover, Del., a cor-- poration of Delaware Application August 31, 1933, 4Serial No., 687,553 io claims. (ci. iss-52) This invention ,relates to the conversion of hydrocarbons `into lmarketable products, both 'low boiling, such as benz'ine, gasoline, kerosene,

naphtha. etc., and high boiling, such as Diesel oil. domestic fuel oil, etc. In certain respects it may be considered as a Afurther'development of or improvement upon the invention set forth in my`\copending application Serial No. 674,129,

filed June 3, 1933, under the title Treatment of hydrocarbons.

One object of the invention is to reduce the amount of equipment required to, effect the desired conversion.I Another object is to convert crude starting materialin a once through operation without internal recycling of any characs ter. Another object is to effect vthe conversion at low or atmospheric pressure'andwith aA minimum input of heat. yOther objects will be apparent fromj the detailed description which follows. Y

The starting material, such as crude oil, topped crude, or the like, is converted in a continuous lonce through operation into the desired low and high boiling liquids, such as a quality gasoline o r motor fuel having a yhigh anti-knock rating and a clean residual oil in the ,gas oil boiling range. The conversion and/or the treatment of the light product is effected by catalytic and other contact masses arranged for periodical regeneration in situ, so that al1 tarry constituents and' coky depositsl are consumed and entirely eliminated vfrom the system during the regenerating periods. The system is arranged for con'- tinuous operation without condensation of intermediate'products, thus avoiding the necessity for a large number of storage. tanks. Pumping equipment is reduced to a minimum by operating `the system under pressure not exceeding pounds per square inch, which is little more than that required to send the charge through the apparatus. Usually a single pump in the feedline to the crude foil` still is utilized to operate the first fractionating tower under some thirty pounds of pressure which is ordinarily suiiicient for the entire system: When the first fractionating tower is voperated atsubstantially atmospheric pressure, additional pumps are neededand are preferably located in some or all of the outlets therefrom. They .may be used to ad-, vantage whenthe system includes apparatus for reforming the heavy. naphthawithr or without the straight run gasoline in order toimprove the octane rating of the lighterhydrocarbons.

In order to illustrate the invention and to` indicate its (operation, concrete embodiments thereof are shown in the accompanying drawings, in which: y

Fig. 1 is a diagrammatic view of a system for converting crude oil; f

Fig. 2 is a similar diagrammatic view of'a mod#` 5 ined system for converting topped crude, treat ing equipment being omitted; and

Fig. 3 is a diagrammatic view similar to Fig. 1 of a system for crude oil which includes op- I tional equipment for reforming straight run gas- 10 oline and heavy naphtha.

In Fig. 1, the charging. material, which is crude petroleum or the equivalent, is forced by a pump 3 into a crude oil still 4 of any suitable or desired type, wherein the starting material is 15 partly vaporized and sent with a minimum of cracking into a fractionating tower 5 which is controlled by cooling coil 6. The light hydrocarbon vapors inthe boiling range of gasoline and gases leave fractionator 5jby a line 1 which contains a back pressure valve 8 bywhich a suitable lowlpressure, normally not exceeding 40 pounds per square inch, is maintained .in fractionator 5.; A liquid side stream, representing a middle or a deep cut, is withdrawn by a valved line 9 and 25 discharged into a heating coil I0 where the material is again vaporized andraised to a superatmospheric temperature within the range of 750 to 950 F. and discharged by suitable valved lines into any one of a series of transforming 30 tower 5 are withdrawn by a valved line Il into 45.

which steam is discharged in suitableamount by branch line- I5, the mixed residuum and steam being discharged by suitable valved connections into any one of aseries of contact vaporizers, of

which two areshown at I6 andlISa. These `Va 50 porizers may be of the `type disclosed in United l States Patent No. 1,806,997, issued 'to `Alfred.

Joseph on May 26, '1931, but preferably of the improved type and arrangement disclosed in my copending application, Serial No. 670,954, filed 55 of which two are shown at 23 and 23a.

May 13, 1933, and issued on February 5, 1935, as Patent No. 1,989,927. These chambers contain suitable inert porous contact masses, such as broken fragments of brick, pieces of pumice,

5 molded units of china clay or other silicates of alumina or clayey materials, or preferably the inert carrier material disclosed in United States Patent No. 1,818,403, issued to Alfred Joseph on August 11, 1931. These contact masses act to remove asphaltic or heavy carbonaceous materials, possibly to some extent at least by absorption, leaving the fluids which pass therefrom in vapor form of a more volatile nature than the residuum or bottoms fed thereto. The tempera- 15 tures ordinarily preferably employed in this contact vaporization are superatmospheric and of the order of 700 to 900 F., or more preferably 790 to 875 F. Often the bottoms introduced into the contact vaporizers can be kept within the desired temperature range without separate heating, except for that supplied by the superheated steam. However, of course it'is contemplated to employ a heater where the same is desirable or necessary. The vaporized products from chambers IB and IGa are discharged by suitable valved connections into line I'I which joins the line leading from heater coil I to catalytic transforming chambers II and Ila or into separate but like chambers, with the result that 30 all of the liquid products of fractionating tower are subjected to the same catalytic transforming operation, the products of which are discharged into fractionating tower I3. The pressures existing in the vaporizing and transforming operations, because of the nature of the apparatus, are approximately the same as but slightly less than those existing in still 4 and fractionator 5. The bottoms from tower I3, which consist of a clean residual oil having the characteristics of a gas oil but of either slightly lighter or heavier gravity than the original charging stock, are withdrawn by valved line I8 to storage tank I9. 'I'he light overhead hydrocarbons passing control coil 20 leave the -top of fractionating tower I3 by a line 2| which joins line 'I carrying the straight run gasoline vapors from fractionating tower 5. A pump or blower (not shown) may be provided in line 2I, if needed, to equalize the pressures in 50 lines 1 and 2|. All these vapors -pass through a heater coil 22 which raises the temperature to the range of 500 to 700 F., and discharges the same through suitable valved connections into" any one of a series of catalytic refining chambers, These chambers contain a porous solid composed to substantial extent of components from the group comprising silicates ofl alumina and clayey materials and may, for example, consist of a molded catalytic material adapted to purify, stabilize,

and refine the light hydrocarbons with a polymerizing action and preferably comprising activated hydrosilicate of alumina to which is added small amounts of metallic oxides, such as copper,

g5 nickel and cobalt. The refined vapors leave chambers 23 and 23a by suitable valved connections to line 24, which discharges into fractionating tower 25 controlled by cooling coil 26. The

. liquid polymers thrown down in thiscolumn are in the form of a clean residual oil, and are conducted by valved line 2B toresidual oil tank '|9. The overhead vapors leave fractionator 25 by line 21, which conducts them through condenser 28, and thence into separator 29, whence tne xed gases leave by line 30, while the condensed prodacreage ucts, such as gasoline or motor fuel, are conducted by valved line 3| into storage tank 32.

The contact vaporizers I6 and I6a, the catalytic transformers II and Ila, and the catalyticreners 23 and 23a are provided in pairs or multiples thereof, to permit continuous operation of the system,-with each member of each group alternately on stream and in regeneration. Regeneration is effected by oxidation, so that all tarry and coky or sulphurous deposits left in any of the contact masses are entirely .eliminated during the regenerating periods. 'I'he regenerating medium, such as air diluted, as required, with steam or ilue gas, may be supplied to contact vaporizers I6 and I6a by valved connections to supply line 33, while the fumes of regeneration are discharged through valved connections to line 34. Similarly, the regenerating medium for catalytic transformers I I and I I a is provided by supply line 35, while the fumes are discharged into line 36. Line 31 supplies the regenerating medium to the catalytic refining chambers 23 and 23a, the fumes being discharged through line 38.

Much of the apparatus disclosed in Fig. 2 conforms to that shown in Fig. 1, and the same reference characters are applied thereto. The system disclosed in Fig. 2, however, is intended to handle topped crude containing little or no material in the gasoline range. Hence the overhead line 'Ia from first fractionating tower 5a carries vapors in the gas oil boiling range which pass back pressure valve 8a. and are discharged into heater coil I0a which discharges, in turn, into the catalytic transforming cases I I and IIa. No side stream is withdrawn from fractionator 5a. The bottoms, as in Fig. 1, are withdrawn by valved line I4, and, after being mixed with steam from line I5 and, if necessary, passed through any suitable heater, not shown, are discharged into contact vaporizers I6 and IGa, and thence into the line leading to transforming cases 'Il and IIa.

The residual oil separated by fractionator I3 goes lto storage tank I9, while the overhead vapors and gases are conducted by line 2l to refining apparatus or to storage, as desired.

Fig. 3 discloses a system having all of the features of Fig. 1, with the same reference characters applied to like parts. 'I'he new features reside in the means for reforming a naphtha'cut from the nrst fractionator with or without the overhead material or straight run gasoline. Optionally, the straight run gasoline, with or without the heavy naphtha cut, may be separated out and later fed to the refining apparatus, if desired. Fig. 3 also indicates the use of pumps in all of the outlet lines from the first fractionator, provision being made for bypassing each pump so that the entire system may operate.under the pressure in the first fractionator maintained by the crude oil feed pump, or, optionally, some or all of the fractions may have further treatment under individual pressure conditions. As indicated, overhead line Ib from first fractionator 5b leads through back pressure valve 8b directly toV bypass connection 48 therearound. Line 44 has a valved connection 41 to the overhead vapor line 1b in advance of back pressure valve 8b.l Line 41 also includes a pump 48 having a valved bypass 49 therearound. The junction of lines 44 and 41 has a valved connection 50 to a heater coil 5I, Where the material fed thereto is raised to a temperature within the range of 800 to 950 Fraud discharged by suitable valved connections into any onel of a series of reforming cases, of which two are shown at 52 and 52a. containing vcatalytic adsorptivematerial capable of reforming the heavy naphtha and overhead hydrocarbons from fractionator 5b into'light products having an improved antiknock rating. The-con Atact material may consist of molded pieces of inert lines 2| and 43 leading to heater 22 ofthe refining apparatus. A lower liquid-. side stream representing a middle or deep cut is lwithdrawn from first fractionator 5b by a valved line 9b leading y to heater I0, and thence to the transforming cases Il and vI I a. Line 9b includes a pump 54 having a valved, bypass '55 ,therearound In .a similar manner, the valved outlet I4b from the bottom of fractionator 5b leading toA contact vaporizers 'I 6 and IBa includes a pump 56 provided with a valved bypass 51 therearound, the same being located in advance o f steam connection i5.

. Heaters I0, Ilia,l 22 and 5I may be of yany suitable or desired type, 'and' heat may be supplied from any suitable source to the coils forming a part thereofm If desired, they may consist of separate coils disposedin vaporizing still4. Since the figures of thel drawings are diagrammaticinI character, 4heat exchangers, coolers. and other apparatus not essential to the understanding of' the invention, are omitted.

All .forms of the invention produce directly from crude starting material, such as crude oil or topped crude, but three nal products, namely,

(l) a residual oil which is clean and suitable for use directly as Diesel oilO or domestic fuel oil, or as-superior charging stock for further cracking operations; (2)- fixed gases resulting from the transforming operatiom' and (3) light liquid hy- "drocarbona' such as motor fuel or gasoline of superior quality and high antiknock characterisv tics, treated or untreated as desired. With the y possible exception of the straight run gasoline, no separationmof intermediate products is made,

so that tanks for such products and subsequent freheating of the 'same may be' entirely avoided.

60 avery moderate `pressure and by effectingl the By operatingthe first fractionating tower under transformingf and/or treating operations at low or atmospheric pressure, the requirements for pumping equipment are vgreatly reduced., 1f pumps other thanv that for thecharging stock may be needed or required, they are locatedin vtheoutlet lines leaving fractionator 5, 5a, or 56,

but pumps at such points are ordinarily 'not necessary, and, if used, may be individually bypassed so that the system has greatfiexibility of opera- .tion.f The'once through continuous operation to 'the final products not only conserves heat by reducingl the required input, but also greatly simplifles refinery practice in production of high quality nnished products. The refining `operation n may be omitted when desired without departingf `from the ,spirit and scope of the invention.

While the invention has been herein disclosed in.what are now considered to be preferred forms L thereof, it is to be understood that the invention is not limited to the specific' details of s uch forms, b ut covers all changes, modifications and adapta.

' tions within the scope of the appended claims.

I claim as my invention: 1. The process of transforming high boiling hydrocarbons intolower boiling hydrocarbons in a continuous operation by contacting the same with s'olidcontact materials capableof effectingl desirable changes therein which comprises separating the hydrocarbon" charge into two fractions of different molecular weights and boiling ranges, the high boiling fraction being vcomposed primarily of heavy hydrocarbons `within the fuel oil range and the low boiling fraction lbeing composedV substantially of hydrocarbons in the gas oil boiling range,subjecting each fraction a separate heating operation to effect vaporization, that on the high boiling fraction being effected by ,contact treatment with a bed of porous con- Vtact materialfuniting the vapors of both fractions, and subjecting the combined vapors to a transforming` operation vbythe actionof active contact material selected from the class consisting of silicates of alumina'and clayey material in the temperature range of 750 to 950 F.

2. The process of treating a crude hydrocarbon fluid of'petroleum originl to produce a high yield of low boiling hydrocarbons in acontinuous operation by contacting the charge with solid contact materials capable of effecting desirable .changes therein -which comprises separating the hydrocarbon charge into a plurality of fractions of different molecular weights and boiling ranges,4 subjecting the low boiling fraction to treatment with a bed of porousv contactmaterial comprising essentially' activatedhydrosilicate of'alumina and* capable of effecting a stabilization of the same. subjecting the other fractions to separate initial heating and vaporizing treatments, each such vaporizing .treatment differing -from the other and one being effected with a bed of porous contact material, uniting the vaporized. fractiok,

transforming the united fractions in vapor phase.

broad range of molecular weights in a continuous operation by contacting thev saine` with beds of solid contact material capable of effecting desirable changes therein including the production of high quality gasoline which comprises separating the hydrocarbon fluid into three fractions of different molecular weights and boiling ranges, subjecting the highest boiling fraction in a continuous stream in successionto contact treatments with three separate beds of contact material underdiiferent conditions and separating and removing from the stream the heaviest products after at least one of the nrst two contact treatments and before the stream passes to the next successive contact treatment, subjectingv the intermediate fraction to the last two of said separatecontactjtreatments along with the products of the first .fraction by adding the latter to theA 75 stream after the-first contact treatment, and subjecting the low boiling fraction to the last of said contact treatments along with the low boiling products from the first two fractions by adding the latter to the stream after the second contact treatment.

4'.V The process of treating a crude hydrocarbon fluid of petroleum origin containing substantial amounts of components both above and below 1c the gas oil range, as well as within said range, by contacting the same with solid contact materials chosen from the class consisting of silicates of alumina and clayey materials, which comprises the continuous operation of separating the hyl drocarbon fluid into a plurality of fractions of diierent molecular weights and boiling ranges, a low boiling fraction which is lighter than gas oil, a high boiling fraction which is heavier than gas oil, and an intermediate fraction including components in the gasoil boiling range, subjecting each fraction at reaction temperature to an initial contact treatment with a bed of solid contact material from the above class under conditions differing from those of the initial contact treatment of the others, the low boiling fraction being treated under conditions so as to reform the same, the high boiling fraction being treated with a bed of porous but relatively yinert material under such conditions as to effect a vaporization of the bulk of the lighter Icomponents thereof, so as to produce a composite material of the nature of a crude petroleum oil, the said intermediate fraction being treated under conditions so as to crack substantial amounts thereof into compoundsI within the gasoline range, and adding products of lower boiling range from each fraction in succession after each contact treatment to the next lighter fraction in advance of a subsequent Contact treatment on the same.

5. The process of treating a crude hydrocarbon fluid of petroleum origin by contacting the same with solid contact materials capable of effecting desirable changes therein which comprises separating the hydrocarbon fluid primarily into three fractions of different molecular and boiling ranges, the high boiling fraction having-a rangeabove a temperature of the order of '750 F., the low boiling fraction having a boiling range 60 below a temperature of the order of 425 F. and

theintermediate fraction having a range intermediate the other two, contacting the said high boiling fraction with a contact material capable of producing therefrom a substantial proportion of hydrocarbons within the range of the aforesaid intermediate fraction and passing the same into the stream of the said intermediate frac'- tion, passing the combined intermediate fraction into contact with a second bed of.contact material capable of producing therefrom a substantial proportion of hydrocarbons within the range of the aforesaid low-boiling fraction, separating the hydrocarbons so produced from residual hydrocarbons and passing the same into the stream of the aforesaid low-boiling hydrocarbons, and passing the combined stream of low-boiling hydrocarbons into contact with a. contact material capable of stabilizing the same against gum and color formation;

6. The process of treating a crude hydrocarbon fluid of petroleum origin by contacting the same with solid contact materials capable of effecting desirable changes therein which comprises separating the hydrocarbon fluid primarily into three u fractions of different molecular and boiling acreage ranges, the high boiling fraction having 'i range above a temperature of the order of '750 F., the low boiling fraction having a boiling range bclow a temperature of the order of 425 F. and the intermediate fraction having a range intermediate the other two, contacting the said high boiling fraction at superatmospheric temperatures with a contact material having a substantial proportion of components from the group comprising silicates of alumina and clayey materials and capable of producing therefrom a substantial proportion of hydrocarbons within the range of the aforesaid intermediate fraction and passing the same into the stream of the said intermediate fraction; passing 4the combined intermediate fraction'into contact with a second bed of contact material having a substantial proportion of components from the aforesaid group and capable of producing therefrom a substantial proportion of hydrocarbons within the range of the aforesaid low boiling fraction, separating the hydrocarbons so produced from residual hydrocarbons and passing the same into the stream of the aforesaid low-boiling hydrocarbons, and passing the combined stream' of low-boiling hydrocarbons into contact with a contact material having a substantial proportion of components from the aforesaid group and capable of stabilizing the same against gum or color formation.

'7. The process of treating a crude hydrocarbon fluid of petroleum origin by contacting the same with solid contact materials capable of effecting desirable changes therein which comprises separating the hydrocarbon fluid primarily into three fractions of different molecular and boil-` ing ranges, the high boiling fraction having a range above a temperature of the order of 750 F., the low boiling fraction having a boiling range below a temperature of the order of 425 F. and the intermediate fraction having a range intermediate the other two, contacting the said high boiling fraction at superatmospheric temperatures with a contact material composed of a porous, adsorptive solid material from the group comprising silicates of alumina and clayey materials and capable of producing therefrom a substantial proportion of hydrocarbons within the range of the aforesaid intermediate fraction and passing the same into the stream of the said intermediate fraction, passing the combined intermediate fraction into contact with a second bed of contact material composed primarily of an activated hydrosilicate of alumina, capable of producing therefrom a substantial proportion of hydrocarbons within the range of the afore- .bon fluid of petroleum origin by contacting the same with solid contact materials capable of eifecting desirable changes therein which comprises separating the hydrocarbon fluid primarily into three fractions of different molecular and boiling ranges, the high boiling fraction having a range above a temperature of the order of '750 the low-boiling fraction having a boiling range below a temperature of the order of 425 F. and the intermediate fraction having a range interand passing the said low-boiling fraction at a,

intermediate fraction, and passing the same into` the stream of the said intermediate fraction, passing the combined intermediate fraction into contact with a second bed o'f contact material comprising catalytically activated hydrosilicate of alumina, the temperature of contact being of the order of 750 to 950 F., thereby to produce a substantial proportion of hydrocarbons within the range of the aforesaid low-boiling fraction,

temperature of theorder of 500*to 700 F. in contact with a rening catalyst comprising a porous hydrosilicate of alumina, thereby` to stabilize said fraction against gum and color. y

9. Theprocess of converting whole crude hydrocarbon starting material into gasoline, fixed gas, and a clean residual oil in a continuous oncethrough operation without internal recycling which comprises heating and partly vaporizing the whole crude material Without cracking or with a minimum of cracking of the same, passing all the heated material into a fractionating zone and therein continuously separating the same into overhead, at least two side streams, and bottoms, subjecting the upper side stream to a reforming operation in vapor phase in the temperature range of 800 to 950 F. to improve the vaporizat-ion and anti-knock characteristics of the lighter hydrocarbons which are in the gasoline boiling range, vaporizing and transforming.

the lower side stream in the temperature range of 750 to 950 F. in contact with a bed of catalytic material containing a substantial proportion material in the gasoline boiling range and a clean residual oil having the properties and characteristics of gas oil and Diesel oil, combining the material in the gasoline boiling range from all of the above operations, and refining and' stabilizing said combined gasoline material in the temperature range of 500 to '700 F. in contact with i a b ed of catalytic material which'contains activated hydrosilicate of alumina.

10. Theprocess of converting whole crude hydrocarbon starting material into motor fuel of the gasoline type, xed gases, and a clean residual oil without the recovery of any coky or tarry material in arcontinuous once through operation without any internal recycling which comprises heating and partly vaporizing the whole.v crude material, passing all the heated material into a fractionating zone and thereinv separating the same into overhead, at least two side streams and bottoms, subjecting the upper side stream to a reforming operation in vapor phase in the temperature range of 800 to 950 F. to improve the antiknock characteristics `of the lighter hydrocarbons, vaporizing and transformingthe lower sidev stream in the temperature range of 750 to 950 F. in contact with a bed of catalytic material comprising or containing activatedk hydrosilicate of alumina, vaporizing the bottoms in contact with a bed of relatively inert but porous absorptive material and then adding the resulting vaporsto the vaporized lower side stream for catalytic transformation with the latinto overhead material in the gasoline boiling range and a clean residualoil having `the properties and characteristics of gas oil or Diesel oil, condensing and combining the lighter hydrocarbons resulting from the above operations to secure a. gasoline type motor fuel and to separate therefrom the xed gases, and regenerating the. catalytic masses by oxidation from time to time as required to remove coky and tarry deposits therefrom without interfering with the continuity of the process.

EUGENE J. HOUDRY. 

